JP7283274B2 - resin composition - Google Patents

Description

The present invention relates to resin compositions containing epoxy resins. Furthermore, it relates to a cured product, a sheet-like laminated material, a resin sheet, a printed wiring board, and a semiconductor device obtained using the resin composition.

2. Description of the Related Art As a technique for manufacturing printed wiring boards, a manufacturing method using a build-up method in which insulating layers and conductor layers are alternately stacked is known. In the build-up manufacturing method, the insulating layer is generally formed by curing a resin composition.

Since printed wiring boards are exposed to various environments such as high and low temperatures, if the linear thermal expansion coefficient of the cured material used for the insulating layer is high, the insulating layer will repeatedly expand and contract, and cracks will occur due to the distortion. . As a technique for keeping the coefficient of linear thermal expansion low, a method of adding an inorganic filler to a cured material is known (Patent Document 1). However, when an inorganic filler is blended into the cured material, the elastic modulus increases, making it difficult to suppress warping.

Further, it has been found that the adhesion between a conductor layer such as a copper foil and an insulating layer decreases when an inorganic filler is contained in the cured material. Due to the recent demand for smaller semiconductor chip packages, excellent adhesion is required.

Further, in recent years, further improvements in the insulation reliability of the insulating layer and in the formability of small-diameter vias have been demanded.

On the other hand, an epoxy resin composition containing an elastomer has been known so far (Patent Documents 2 and 3).

JP 2016-27097 A JP 2019-38969 A International Publication No. 2008/153208

An object of the present invention is to provide a resin composition or the like that can suppress warpage of a cured product and achieve excellent insulation reliability, adhesion, and small-diameter via formability.

In order to achieve the object of the present invention, the present inventors have made intensive studies and found that (A) an epoxy resin, (B) an inorganic filler, (C) a particulate or non-particulate elastomer, and (B) component has a specific surface area of 10 m ² /g or more, the content of component (C) is 35% by mass or less (ratio of components excluding component (B)), and the average particle size of component (C) is 0.8 μm or less By using the resin composition, it is possible to suppress the warpage of the cured product, and to obtain excellent insulation reliability, adhesion, and small-diameter via formability, and have completed the present invention.

That is, the present invention includes the following contents.
[1] A resin composition comprising (A) an epoxy resin, (B) an inorganic filler, and (C) a particulate or non-particulate elastomer,
(B) component has a specific surface area of 10 m ² /g or more,
The content of the component (C) is 35% by mass or less when the non-volatile components other than the component (B) in the resin composition are 100% by mass,
A resin composition wherein, when the component (C) is particulate, the average particle size of the component (C) is 0.8 μm or less.
[2] The resin composition according to [1] above, wherein the component (B) has a specific surface area of 20 m ² /g or more.
[3] The resin composition according to [1] or [2] above, wherein the component (B) is silica.
[4] Any of the above [1] to [3], wherein the content of the component (C) is 25% by mass or less when the non-volatile components other than the component (B) in the resin composition are 100% by mass. The resin composition according to .
[5] Any of the above [1] to [4], wherein the content of the component (C) is 1% by mass or more when the non-volatile components other than the component (B) in the resin composition are 100% by mass. The resin composition according to .
[6] Component (C) is a particulate elastomer, and the particulate elastomer includes styrene-butadiene rubber particles, isoprene rubber particles, butadiene rubber particles, chloroprene rubber particles, acrylonitrile-butadiene rubber particles, butyl rubber particles, and ethylene-propylene rubber. At least one selected from the group consisting of particles, urethane rubber particles, silicone rubber particles, chlorosulfonated polyethylene rubber particles, chlorinated polyethylene rubber particles, acrylic rubber particles, epichlorohydrin rubber particles, polysulfide rubber particles, and fluororubber particles. The resin composition according to any one of [1] to [5] above, including one.
[7] Component (C) is a non-particulate elastomer, and the non-particulate elastomer has a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, and a polyisoprene structure in its molecule. , a polyisobutylene structure, and a polycarbonate structure.
[8] The resin composition according to [7] above, wherein the non-particulate elastomer contains a polybutadiene resin.
[9] The resin composition according to [8] above, wherein the non-particulate elastomer contains at least one selected from the group consisting of phenolic hydroxyl group-containing polybutadiene resins and epoxy group-containing polybutadiene resins.
[10] The resin composition according to any one of [1] to [9] above, further comprising (D) a curing agent.
[11] The resin composition according to [10] above, wherein the component (D) contains an active ester curing agent.
[12] The above [10] or [11], wherein the content of the component (D) is 30% by mass or more when the non-volatile components other than the component (B) in the resin composition are 100% by mass. of the resin composition.
[13] A cured product of the resin composition according to any one of [1] to [12] above.
[14] A sheet-like laminate material containing the resin composition according to any one of [1] to [12] above.
[15] A resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of [1] to [12] provided on the support.
[16] A printed wiring board comprising an insulating layer comprising a cured product of the resin composition according to any one of [1] to [12] above.
[17] A semiconductor device including the printed wiring board according to [16] above.

ADVANTAGE OF THE INVENTION According to the resin composition of this invention, it can suppress the curvature of a hardened|cured material, and can achieve the outstanding insulation reliability, adhesiveness, and small diameter via formation property.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will now be described in detail with reference to its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified without departing from the scope of the claims of the present invention and their equivalents.

<Resin composition>
The resin composition of the present invention contains (A) an epoxy resin, (B) an inorganic filler, and (C) a particulate or non-particulate elastomer, and component (B) has a specific surface area of 10 m ² /g or more. , the content of component (C) is 35% by mass or less (ratio of components excluding component (B)), and the average particle size of component (C) is 0.8 μm or less. By using such a resin composition, warping of the cured product can be suppressed, and excellent insulation reliability, adhesion, and small-diameter via formability can be achieved.

The resin composition of the present invention may further contain optional components in addition to (A) an epoxy resin, (B) an inorganic filler, and (C) a particulate or non-particulate elastomer. Examples of optional components include (D) a curing agent, (E) a curing accelerator, (F) a flame retardant, (G) a thermoplastic resin, (H) other additives, and (I) an organic solvent. be done. Each component contained in the resin composition will be described in detail below.

<(A) Epoxy resin>
The resin composition of the present invention contains (A) an epoxy resin. (A) Epoxy resin means a resin having an epoxy group. However, (A) the epoxy resin does not include those corresponding to the (C) component.

(A) Epoxy resins include, for example, bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, and trisphenol type epoxy resins. Epoxy resin, naphthol novolak type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin , cresol novolak type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, tri Methylol-type epoxy resins, tetraphenylethane-type epoxy resins, and the like are included. Epoxy resins may be used singly or in combination of two or more.

(A) The epoxy resin preferably has two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin is 100 mass %, at least 50 mass % or more of the epoxy resin preferably has two or more epoxy groups in one molecule. Among them, the resin composition includes a liquid epoxy resin at a temperature of 20° C. (hereinafter also referred to as a “liquid epoxy resin”) and a solid epoxy resin at a temperature of 20° C. (hereinafter also referred to as a “solid epoxy resin”). A combination is preferred. A liquid epoxy resin having two or more epoxy groups in one molecule is preferable as the liquid epoxy resin. As the solid epoxy resin, a solid epoxy resin having 3 or more epoxy groups in one molecule is preferable.

Examples of liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, and an ester skeleton. An alicyclic epoxy resin, a cyclohexane-type epoxy resin, a cyclohexanedimethanol-type epoxy resin, and a glycidylamine-type epoxy resin are preferable, and a naphthalene-type epoxy resin and a bisphenol A-type epoxy resin are more preferable.

Specific examples of liquid epoxy resins include "HP-4032", "HP-4032D", and "HP-4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US" and "jER828EL" manufactured by Mitsubishi Chemical Corporation; "825", "Epikote 828EL" (bisphenol A type epoxy resin), "jER807", "1750" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "630", "630LSD" ( Glycidylamine type epoxy resin); "ZX1059" manufactured by Nippon Steel Chemical & Materials Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" manufactured by Nagase ChemteX Corporation (glycidyl ester type epoxy resin); "CEL2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel; "ZX1658" and "ZX1658GS" manufactured by Nippon Steel Chemical & Materials (liquid 1,4-glycidylcyclohexane type epoxy resin) Mitsubishi Chemical Corporation "630LSD" (glycidylamine type epoxy resin); DIC Corporation "EXA-850CRP" (bisphenol A type epoxy resin); ADEKA Corporation "EP-3950S", "EP-3980S" ( Glycidylamine type epoxy resin); "ELM-100H" (glycidylamine type epoxy resin) manufactured by Sumitomo Chemical Co., Ltd., and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, and tetraphenylethane type epoxy resin are preferable, and biphenyl type epoxy resin and bixylenol type epoxy resin are more preferable. preferable.

Specific examples of solid epoxy resins include "HP-4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" manufactured by DIC (naphthalene type tetrafunctional epoxy resin); DIC's "N-690" (cresol novolac type epoxy resin); DIC's "N-695" (cresol novolak type epoxy resin); DIC's "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin); DIC's "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000L" ", "HP6000" (naphthylene ether type epoxy resin); Nippon Kayaku "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku "NC7000L" (naphthol novolac type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku; "ESN475V" (naphthalene type epoxy resin) manufactured by Nippon Steel Chemical &Materials; Materials Co., Ltd. "ESN485" (naphthol novolac type epoxy resin); Mitsubishi Chemical Corporation "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin); Mitsubishi Chemical Corporation "YX4000HK" (bixylenol type epoxy resin); "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Co.; "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals; "YL7760" manufactured by Mitsubishi Chemical (bisphenol AF type epoxy Resin); "YL7800" manufactured by Mitsubishi Chemical Corporation (fluorene type epoxy resin); "jER1010" manufactured by Mitsubishi Chemical Corporation (solid bisphenol A type epoxy resin); "jER1031S" manufactured by Mitsubishi Chemical Corporation (tetraphenylethane type epoxy resin) and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types.

When a liquid epoxy resin and a solid epoxy resin are used together as component (A), the ratio by mass (liquid epoxy resin: solid epoxy resin) is 1:0.01 to 1:20. Ranges are preferred, with a range of 1:0.1 to 1:10 being more preferred, and a range of 1:1 to 1:5 being even more preferred.

The epoxy equivalent of component (A) is preferably 50 g/eq. ~5000g/eq. , more preferably 50 g/eq. ~3000g/eq. , more preferably 80 g/eq. ~2000 g/eq. , even more preferably 110 g/eq. ~1000g/eq. is. Within this range, the crosslink density of the cured product of the resin sheet is sufficient, and an insulating layer with a small surface roughness can be obtained. Epoxy equivalent weight is the mass of resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of component (A) is preferably 100 to 5,000, more preferably 250 to 3,000, still more preferably 400 to 1,500. Here, the weight average molecular weight of the epoxy resin is the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

The content of (A) the epoxy resin is not particularly limited, but when the non-volatile components excluding the (B) inorganic filler in the resin composition is 100% by mass, it is preferably 10% by mass or more, and more It is preferably 20% by mass or more, more preferably 30% by mass or more, and particularly preferably 35% by mass or more. Although the upper limit of the content of (A) the epoxy resin is not particularly limited, it is preferably 90% by mass or less when the non-volatile components excluding (B) the inorganic filler in the resin composition are 100% by mass. , more preferably 70% by mass or less, still more preferably 60% by mass or less, and particularly preferably 50% by mass or less.

<(B) Inorganic filler>
The resin composition of the present invention contains (B) an inorganic filler. In the present invention, the specific surface area of (B) the inorganic filler is 10 m ² /g or more. (B) The inorganic filler is contained in the resin composition in the form of particles.

(B) An inorganic compound is used as the material of the inorganic filler. (B) Examples of inorganic filler materials include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and water. Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly preferable from the viewpoint of obtaining the desired effect of the present invention remarkably. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. As silica, spherical silica is preferable. (B) The inorganic filler may be used singly or in combination of two or more at any ratio. When two or more kinds of inorganic fillers are contained in the resin composition of the present invention, the total specific surface area of all inorganic fillers should be 10 m ² /g or more.

(B) The inorganic filler has a specific surface area of 10 m ² /g or more, preferably 15 m ² /g or more, more preferably 18 m ² /g or more, particularly from the viewpoint of significantly obtaining the desired effects of the present invention. It is preferably 20 m ² /g or more. (B) ^The upper limit of the specific surface area ^of the ^inorganic filler is not ^particularly limited ^. g or less, 30 m ² /g or less, 25 m ² /g or less, and the like. (B) The specific surface area of the inorganic filler is determined by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method, and using the BET multipoint method to determine the specific surface area. is obtained by calculating

The average particle size of the inorganic filler (B) is not particularly limited, but is preferably 0.05 μm or more, more preferably 0.1 μm or more, still more preferably 0.12 μm or more, and particularly preferably 0.14 μm. That's it. (B) The upper limit of the average particle size of the inorganic filler is not particularly limited, but is preferably 10.0 μm or less and 5.0 μm or less, more preferably 3.0 μm or less and 2.0 μm or less, and still more preferably is 1.0 μm or less, 0.7 μm or less, particularly preferably 0.5 μm or less, 0.3 μm or less.

(B) The average particle size of the particles of the inorganic filler can be measured by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, a particle size distribution of particles can be prepared on a volume basis using a laser diffraction/scattering type particle size distribution measuring apparatus, and an average particle size can be measured as a median size from the particle size distribution. As the measurement sample, particles dispersed in a solvent such as water by ultrasonic waves can be preferably used. As the laser diffraction/scattering type particle size distribution analyzer, "LA-500" manufactured by Horiba Ltd., "SALD-2200" manufactured by Shimadzu Corporation, etc. can be used.

(B) Inorganic fillers include, for example, "UFP-20", "UFP-30" and "SFP-20M" manufactured by Denka; Silfil NSS-5N"; Admatechs "SO-C1", "SO-E1", "YC100C", "YA050C", "YA010C" and the like.

(B) The inorganic filler is preferably surface-treated with an appropriate surface-treating agent. The surface treatment can enhance the moisture resistance and dispersibility of the (B) inorganic filler. Examples of surface treatment agents include vinyl silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane. , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and other epoxy-based silane coupling agents; p-styryltrimethoxysilane and other styryl-based Silane coupling agents; Methacrylic silane coupling agents such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane; Acrylic silane coupling agents such as 3-acryloxypropyltrimethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane , 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N - Amino silane coupling agents such as phenyl-8-aminooctyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; tris-(trimethoxysilylpropyl) isocyanurate, etc. isocyanurate-based silane coupling agents; ureido-based silane coupling agents such as 3-ureidopropyltrialkoxysilane; mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane ; isocyanate-based silane coupling agents such as 3-isocyanatopropyltriethoxysilane; acid anhydride-based silane coupling agents such as 3-trimethoxysilylpropylsuccinic anhydride; silane coupling agents such as; methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltri Non-silane coupling-alkoxysilane compounds such as ethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, trifluoropropyltrimethoxysilane, and the like are included. The surface treatment agents may be used singly or in combination of two or more at any ratio.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the (B) inorganic filler. (B) The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, from the viewpoint of improving the dispersibility of the (B) inorganic filler. Particularly preferably, it is 0.2 mg/m ² or more. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin composition and the melt viscosity in the form of a sheet, the amount of carbon is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and particularly preferably is less than or equal to 0.5 mg/ ^m2 .

The amount of carbon per unit surface area of the (B) inorganic filler is measured after the surface-treated (B) inorganic filler is washed with a solvent (for example, methyl ethyl ketone (hereinafter sometimes abbreviated as “MEK”)). , can be measured. Specifically, a sufficient amount of methyl ethyl ketone and the (B) inorganic filler surface-treated with a surface treatment agent are mixed, and ultrasonically cleaned at 25° C. for 5 minutes. Thereafter, after removing the supernatant liquid and drying the solid content, the amount of carbon per unit surface area of the (B) inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Ltd. can be used.

The content of the (B) inorganic filler in the resin composition is not particularly limited. It is 20% by mass or more, more preferably 30% by mass or more, and particularly preferably 40% by mass or more. (B) The upper limit of the content of the inorganic filler is not particularly limited. Below, more preferably 80% by mass or less, particularly preferably 70% by mass or less.

<(C) Particulate or non-particulate elastomer>
The resin composition of the present invention contains (C) a particulate or non-particulate elastomer. In the present invention, the elastomer means a resin having flexibility, a particulate resin component (particulate elastomer) that maintains the form of particles in the resin composition, or an irregular shape that tends to be mixed or dissolved in the resin composition. A non-particulate resin component (non-particulate elastomer) that exhibits rubber elasticity or a resin that reacts with other components to exhibit rubber elasticity is preferred. Examples of resins exhibiting rubber elasticity include resins exhibiting a modulus of elasticity of 1 GPa or less when subjected to a tensile test at a temperature of 25° C. and a humidity of 40% RH in accordance with Japanese Industrial Standards (JIS K7161). be done.

The particulate elastomer is preferably spherical.

Examples of particulate elastomers include styrene-butadiene rubber (SBR) particles, isoprene rubber (IR) particles (including natural rubber (NR) particles), butadiene rubber (BR) particles, chloroprene rubber (CR) particles, acrylonitrile rubber (CR) particles, Diene rubber particles such as butadiene rubber (NBR) particles (including hydrogenated nitrile rubber (HNBR) particles); butyl rubber (IIR) particles, ethylene-propylene rubber (EPM) particles (ethylene-propylene-diene rubber (EPDM) particles ), urethane rubber (U) particles (including polyester urethane rubber (AU) particles, polyether urethane rubber (EU) particles), silicone rubber (Q) particles (methyl silicone rubber (MQ) particles, vinyl methyl silicone rubber (VMQ) particles, phenyl methyl silicone rubber (PMQ) particles, fluorosilicone rubber (FVMQ) particles), chlorosulfonated polyethylene rubber (CSM) particles, chlorinated polyethylene rubber (CM) particles, acrylic rubber (ACM, ANM) particles, epichlorohydrin rubber (CO) particles (including epichlorohydrin/ethylene oxide rubber (ECO) particles), polysulfide rubber (T) particles, fluororubber (FKM) particles (tetrafluoroethylene/propylene rubber (FEPM) particles, tetrafluoroethylene-purple orovinyl ether rubber (FFKM) particles) and other non-diene rubber particles, preferably urethane rubber particles.

Examples of particulate elastomers include "MM-101SM (average particle size 0.07 to 0.1 μm)" and "MM-101SMA (average particle size 0.1 to 0.2 μm)" (urethane Rubber particles); Mitsubishi Rayon "Metabrene W300A (average particle size 0.1 μm)", "W450A (average particle size 0.2 μm)" (acrylic rubber particles); JSR "XER-91 (average particle size diameter 0.5 μm)” (acrylonitrile-butadiene rubber particles); JSR’s “XSK-500 (average particle diameter 0.5 μm)” (styrene-butadiene rubber particles), etc. These may be used alone or in combination of two types. The above can be used in combination.

The average particle size of the particulate elastomer is 0.8 μm or less, and from the viewpoint of significantly obtaining the desired effects of the present invention, it is preferably 0.5 μm or less, more preferably 0.3 μm or less, and particularly preferably 0.2 μm. It is below. The lower limit of the average particle size of the particulate elastomer is not particularly limited, and may be, for example, 0.005 μm or more, 0.01 μm or more, 0.03 μm or more, 0.05 μm or more. The average particle size of the particulate elastomer used in the present invention can be measured using dynamic light scattering. For example, rubber particles are uniformly dispersed in an appropriate organic solvent using ultrasonic waves or the like, and the particle size distribution of the rubber particles is prepared on a mass basis using a concentrated particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.). and the mass-based median diameter (d50) is taken as the average particle diameter.

The non-particulate elastomer has at least one selected from a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule. From the viewpoint of obtaining a flexible material, it is more preferably a resin having one or more structures selected from a polybutadiene structure and a polycarbonate structure. Polybutadiene resin, which is a resin possessed in the above, is particularly preferred. In addition, "(meth)acrylate" refers to methacrylate and acrylate.

The polybutadiene structure includes not only a structure formed by polymerizing butadiene but also a structure formed by hydrogenating the structure. Also, the butadiene structure may be partially hydrogenated or entirely hydrogenated. Furthermore, the polybutadiene structure may be included in the main chain or side chains in the non-particulate elastomer.

Preferred examples of polybutadiene resins include hydrogenated polybutadiene skeleton-containing resins, hydroxyl group-containing polybutadiene resins, phenolic hydroxyl group-containing polybutadiene resins, carboxyl group-containing polybutadiene resins, acid anhydride group-containing polybutadiene resins, epoxy group-containing polybutadiene resins, isocyanate group-containing polybutadiene resins, containing polybutadiene resin, urethane group-containing polybutadiene resin, and the like. Among them, a phenolic hydroxyl group-containing polybutadiene resin and an epoxy group-containing polybutadiene resin are more preferable. Here, the "hydrogenated polybutadiene skeleton-containing resin" refers to a resin in which at least a portion of the polybutadiene skeleton is hydrogenated, and does not necessarily have to be a resin in which the polybutadiene skeleton is completely hydrogenated. Examples of hydrogenated polybutadiene skeleton-containing resins include hydrogenated polybutadiene skeleton-containing epoxy resins. Examples of preferred phenolic hydroxyl group-containing polybutadiene resins include those made from hydroxyl group-terminated polybutadiene, diisocyanate compounds and phenolic hydroxyl group-containing resins. Examples of the hydroxyl group-terminated polybutadiene and diisocyanate compounds are the same as those exemplified below. Examples of phenolic hydroxyl group-containing resins include cresol novolac resins.

Specific examples of polybutadiene resins include "PB-3600" (epoxy group-containing polybutadiene) manufactured by Daicel Corporation, "JP-100" and "JP-200" (epoxy group-containing polybutadiene) manufactured by Nippon Soda Co., Ltd., and Clay Valley Co., Ltd. "Ricon 657" (epoxy group-containing polybutadiene), "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", "Ricon 131MA20", "Ricon 184MA6" (acid anhydride group-containing polybutadiene), "GQ-1000" (hydroxyl group- and carboxyl group-introduced polybutadiene), "G-1000", "G-2000", "G-3000" (polybutadiene with hydroxyl groups at both ends), " GI-1000", "GI-2000", "GI-3000" (hydrogenated polybutadiene at both ends), Daicel's "PB3600", "PB4700" (polybutadiene skeleton epoxy compound), "Epofriend A1005", " Epofriend A1010", "Epofriend A1020" (epoxy compound of styrene, butadiene and styrene block copolymer), "FCA-061L" (hydrogenated polybutadiene skeleton epoxy compound) manufactured by Nagase ChemteX Corporation, "R-45EPT" (polybutadiene skeleton epoxy compound) and the like.

Examples of preferred polybutadiene resins include linear polyimides made from hydroxyl group-terminated polybutadiene, diisocyanate compounds and polybasic acids or their anhydrides (Japanese Patent Application Laid-Open No. 2006-37083, International Publication No. 2008/153208). polyimide). The polybutadiene structure content of the polyimide resin is preferably 60% to 95% by mass, more preferably 75% to 85% by mass. Details of the polyimide resin can be referred to in JP-A-2006-37083 and WO 2008/153208, the contents of which are incorporated herein.

The number average molecular weight of the hydroxyl-terminated polybutadiene is preferably 500-5,000, more preferably 800-3,500. The hydroxyl group equivalent of the hydroxyl group-terminated polybutadiene is preferably 250 to 5,000 g/eq. , more preferably 1,000 to 3,000 g/eq. is.

Examples of diisocyanate compounds include aromatic diisocyanates such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylylene diisocyanate and diphenylmethane diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate; and alicyclic compounds such as isophorone diisocyanate. diisocyanates of the formula: Among these, aromatic diisocyanates are preferred, and toluene-2,4-diisocyanate is more preferred.

Examples of polybasic acids or anhydrides thereof include ethylene glycol bis-trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, naphthalenetetracarboxylic acid, 5-(2,5-dioxotetrahydrofuryl)- Tetrabasic acids such as 3-methyl-cyclohexene-1,2-dicarboxylic acid and 3,3′-4,4′-diphenylsulfonetetracarboxylic acid and their anhydrides, and tribasic acids such as trimellitic acid and cyclohexanetricarboxylic acid Acids and their anhydrides, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho(1,2-C)furan-1,3 - dione and the like.

Also, the polybutadiene resin may include a polystyrene structure having a structure obtained by polymerizing styrene.

Specific examples of polystyrene resins, which are resins having a polystyrene structure in the molecule, include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene- Styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-butadiene-butylene-styrene block copolymer polymer (SBBS), styrene-butadiene diblock copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoprene block copolymer, hydrogenated styrene-butadiene random copolymer and the like.

Commercially available polystyrene resins may be used, for example, hydrogenated styrene thermoplastic elastomer "H1041", "Tuftec H1043", "Tuftec P2000", "Tuftec MP10" (manufactured by Asahi Kasei Corporation); epoxidized styrene-butadiene Thermoplastic elastomers "Epofriend AT501" and "CT310" (manufactured by Daicel); Modified styrene elastomer having hydroxyl group "Septon HG252" (manufactured by Kuraray); Modified styrene elastomer having carboxyl group "Tuftec N503M", amino modified styrene elastomer "Tuftec N501" having an acid anhydride group; modified styrene elastomer "Tuftec M1913" (manufactured by Asahi Kasei Chemicals); unmodified styrene elastomer "Septon S8104" (manufactured by Kuraray Co., Ltd.); be able to. (C) component may be used individually by 1 type, and may be used in combination of 2 or more types.

A polysiloxane structure is a structure containing siloxane bonds, and is included in, for example, silicone rubber. The polysiloxane structure may be contained in the main chain or side chains in the non-particulate elastomer molecule.

Specific examples of the polysiloxane resin, which is a resin having a polysiloxane structure in the molecule, include "SMP-2006", "SMP-2003PGMEA", and "SMP-5005PGMEA" manufactured by Shin-Etsu Silicone Co., Ltd., amine group-terminated polysiloxane, Linear polyimides made from basic acid anhydrides (International Publication No. 2010/053185) and the like can be mentioned.

A poly(meth)acrylate structure is a structure formed by polymerizing acrylic acid or an acrylic acid ester, and includes a structure formed by polymerizing methacrylic acid or a methacrylic acid ester. The (meth)acrylate structure may be contained in the main chain or in the side chain in the non-particulate elastomer molecule.

Preferable examples of poly(meth)acrylate resins, which are resins having a poly(meth)acrylate structure in the molecule, include hydroxyl group-containing poly(meth)acrylate resins, phenolic hydroxyl group-containing poly(meth)acrylate resins, and carboxyl group-containing poly(meth)acrylate resins. Poly(meth)acrylate resins, acid anhydride group-containing poly(meth)acrylate resins, epoxy group-containing poly(meth)acrylate resins, isocyanate group-containing poly(meth)acrylate resins, urethane group-containing poly(meth)acrylate resins, etc.) mentioned.

Specific examples of poly(meth)acrylate resins include Teisan Resin "SG-70L", "SG-708-6", "WS-023", "SG-700AS" and "SG-280TEA" manufactured by Nagase ChemteX Corporation. ”(Carboxy group-containing acrylic acid ester copolymer resin, acid value 5-34 mgKOH / g, weight average molecular weight 400,000-900,000, Tg-30 ° C.-5 ° C.), “SG-80H”, “SG-80H- 3”, “SG-P3” (epoxy group-containing acrylic acid ester copolymer resin, epoxy equivalent 4761-14285 g/eq, weight average molecular weight 350,000-850,000, Tg 11° C.-12° C.), “SG-600TEA”, "SG-790"" (hydroxy group-containing acrylic acid ester copolymer resin, hydroxyl value 20-40 mgKOH/g, weight average molecular weight 500,000-1,200,000, Tg -37°C to -32°C), manufactured by Negami Kogyo Co., Ltd. "ME-2000", "W-116.3" (carboxy group-containing acrylic ester copolymer resin), "W-197C" (hydroxyl group-containing acrylic ester copolymer resin), "KG-25", " KG-3000" (epoxy group-containing acrylic acid ester copolymer resin) and the like.

The polyalkylene structure preferably has a given number of carbon atoms. Specifically, the number of carbon atoms in the polyalkylene structure is preferably 2 or more, more preferably 3 or more, particularly preferably 5 or more, and preferably 15 or less, more preferably 10 or less, and particularly preferably 6 or less. Also, the polyalkylene structure may be contained in the main chain or in the side chain of the non-particulate elastomer molecule.

The polyalkyleneoxy structure preferably has a given number of carbon atoms. Specifically, the number of carbon atoms in the polyalkyleneoxy structure is preferably 2 or more, preferably 3 or more, more preferably 5 or more, preferably 15 or less, more preferably 10 or less, and particularly preferably 6 or less. The polyalkyleneoxy structures may be contained in the main chain or side chains in the non-particulate elastomer molecule.

Specific examples of the polyalkylene resin that is a resin having a polyalkylene structure in the molecule and the polyalkyleneoxy resin that is a resin having a polyalkyleneoxy structure in the molecule include "PTXG-1000" and "PTXG" manufactured by Asahi Kasei Fibers Co., Ltd. -1800”, “YX-7180” manufactured by Mitsubishi Chemical Corporation (resin containing an alkylene structure having an ether bond), “EXA-4850-150”, “EXA-4816”, “EXA-4822” manufactured by DIC Corporation ”, “EP-4000”, “EP-4003”, “EP-4010”, “EP-4011” manufactured by ADEKA, “BEO-60E” manufactured by New Japan Chemical Co., Ltd., “BPO-20E”, Mitsubishi Chemical "YL7175" and "YL7410" manufactured by the company.

The polyisoprene structure may be contained in the main chain or side chains in the non-particulate elastomer molecule. Specific examples of the polyisoprene resin, which is a resin having a polyisoprene structure in its molecule, include "KL-610" and "KL-613" manufactured by Kuraray Co., Ltd., and the like.

The polyisobutylene structure may be included in the main chain or side chains in the non-particulate elastomer molecule. Specific examples of polyisobutylene resins, which are resins having a polyisobutylene structure in the molecule, include Kaneka's "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene- isobutylene diblock copolymer) and the like.

The polycarbonate structure may be included in the main chain or side chains in the non-particulate elastomer molecule.

Preferable examples of polycarbonate resins, which are resins having a polycarbonate structure in the molecule, include hydroxyl group-containing polycarbonate resins, phenolic hydroxyl group-containing polycarbonate resins, carboxy group-containing polycarbonate resins, acid anhydride group-containing polycarbonate resins, and epoxy group-containing polycarbonate resins. , isocyanate group-containing polycarbonate resins, urethane group-containing polycarbonate resins, and the like.

Specific examples of polycarbonate resins include "T6002" and "T6001" (polycarbonate diols) manufactured by Asahi Kasei Chemicals, and "C-1090", "C-2090" and "C-3090" (polycarbonate diols) manufactured by Kuraray Co., Ltd. etc.

Examples of preferred polycarbonate resins also include linear polyimides made from hydroxyl group-terminated polycarbonates, diisocyanate compounds and polybasic acids or their anhydrides. The linear polyimide has a urethane structure and a polycarbonate structure. The polycarbonate structure content of the polyimide resin is preferably 60% to 95% by mass, more preferably 75% to 85% by mass. Details of the polyimide resin can be referred to in International Publication No. 2016/129541, the contents of which are incorporated herein.

The number average molecular weight of the hydroxyl group-terminated polycarbonate is preferably 500-5,000, more preferably 1,000-3,000. The hydroxyl group-terminated polycarbonate preferably has a hydroxyl group equivalent weight of 250 to 1,250.

The non-particulate elastomer preferably further has an imide structure. By having an imide structure, the heat resistance of the non-particulate elastomer can be enhanced and the crack resistance can be effectively enhanced.

The non-particulate elastomer may be linear, branched or cyclic in structure, preferably linear.

The non-particulate elastomer preferably further has a functional group capable of reacting with component (A). The functional groups also include reactive groups that appear upon heating. When the non-particulate elastomer has a functional group, the mechanical strength of the cured product of the resin composition can be improved.

Functional groups include carboxy groups, hydroxy groups, acid anhydride groups, phenolic hydroxyl groups, epoxy groups, isocyanate groups, urethane groups, and the like. Among them, from the viewpoint of significantly obtaining the effects of the present invention, the functional group has one or more functional groups selected from a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group. is preferred, and a phenolic hydroxyl group is particularly preferred.

The non-particulate elastomer may be used singly or in combination of two or more.

Specific number average molecular weight Mn of the non-particulate elastomer is preferably 500 or more, more preferably 800 or more, still more preferably 1,000 or more, particularly preferably 1,200 or more, and preferably 100,000 or less. More preferably 50,000 or less, particularly preferably 10,000 or less. The number average molecular weight Mn of the non-particulate elastomer is a polystyrene equivalent number average molecular weight measured using GPC (gel permeation chromatography).

When the non-particulate elastomer has functional groups, the functional group equivalent of the non-particulate elastomer is preferably 100 g/eq. above, more preferably 200 g/eq. above, more preferably 1,000 g/eq. above, particularly preferably 2,500 g/eq. or more, preferably 50,000 g/eq. Below, more preferably 30,000 g/eq. Below, more preferably 10,000 g/eq. Below, particularly preferably 5,000 g/eq. It is below. Functional group equivalent weight is the number of grams of resin containing one gram equivalent of functional group. For example, the epoxy group equivalent can be measured according to JIS K7236. Further, for example, the hydroxyl equivalent can be calculated by dividing the molecular weight of KOH by the hydroxyl value measured according to JIS K1557-1.

(C) The glass transition temperature (Tg) of the particulate or non-particulate elastomer is preferably 20° C. or lower, more preferably 10° C. or lower, and even more preferably 0° C. or lower.

(C) The content of the particulate or non-particulate elastomer is 35% by mass or less when the non-volatile components excluding (B) the inorganic filler in the resin composition is 100% by mass, and is the desired content of the present invention. From the viewpoint of significantly obtaining the effect of (1), the content is preferably 30% by mass or less, more preferably 27% by mass or less, and particularly preferably 25% by mass or less. The lower limit of the content of the particulate or non-particulate elastomer (C) is not particularly limited, but when the non-volatile component (B) excluding the inorganic filler in the resin composition is 100% by mass, It is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, and particularly preferably 5% by mass or more.

<(D) Curing agent>
The resin composition of the present invention may contain (D) a curing agent as an optional component. (D) The curing agent has a function of curing the (A) epoxy resin.

(D) The curing agent is not particularly limited, but examples include phenol-based curing agents, naphthol-based curing agents, acid anhydride-based curing agents, active ester-based curing agents, benzoxazine-based curing agents, and cyanate esters. hardeners and carbodiimide hardeners. (D) The curing agent preferably contains an active ester curing agent. The curing agent may be used singly or in combination of two or more.

As the phenolic curing agent and the naphtholic curing agent, a phenolic curing agent having a novolac structure or a naphtholic curing agent having a novolac structure is preferable from the viewpoint of heat resistance and water resistance. From the viewpoint of adhesion to adherends, a nitrogen-containing phenolic curing agent or a nitrogen-containing naphthol curing agent is preferable, and a triazine skeleton-containing phenolic curing agent or a triazine skeleton-containing naphthol curing agent is more preferable. Among them, a triazine skeleton-containing phenol novolak resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion. Specific examples of phenol-based curing agents and naphthol-based curing agents include "MEH-7700", "MEH-7810" and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., "NHN" manufactured by Nippon Kayaku Co., Ltd., "CBN", "GPH", Nippon Steel Chemical & Materials "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495" ”, “SN-375”, “SN-395”, DIC “LA-7052”, “LA-7054”, “LA-3018”, “LA-3018-50P”, “LA-1356”, "TD2090", "TD-2090-60M" and the like.

Acid anhydride curing agents include curing agents having one or more acid anhydride groups in one molecule. Specific examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and hydrogenated methylnadic acid. anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trianhydride mellitic acid, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'- Diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1 , 3-dione, ethylene glycol bis(anhydrotrimellitate), polymer-type acid anhydrides such as styrene/maleic acid resin obtained by copolymerizing styrene and maleic acid. Commercially available acid anhydride curing agents include "HNA-100" and "MH-700" manufactured by Shin Nippon Rika.

The active ester-based curing agent is not particularly limited, but generally contains an ester group with high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds in one molecule. A compound having two or more is preferably used. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, Benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolak, and the like. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Specifically, an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolak are preferred. Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. "Dicyclopentadiene-type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentalene-phenylene.

Commercially available active ester curing agents include, as active ester compounds containing a dicyclopentadiene type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", " HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM" (manufactured by DIC); active ester compounds containing a naphthalene structure "EXB9416-70BK", "HPC-8150-60T", "EXB-8150-65T" (manufactured by DIC); "DC808" as an active ester compound containing acetylated phenol novolac (manufactured by Mitsubishi Chemical Corporation); phenol novolak "YLH1026" (Mitsubishi Chemical Co., Ltd.) as an active ester compound containing a benzoylated product of phenol; "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1030" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd.);

Specific examples of benzoxazine-based curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; Examples include "Fa".

Examples of cyanate ester curing agents include bisphenol A dicyanate, polyphenolcyanate (oligo(3-methylene-1,5-phenylenecyanate)), 4,4'-methylenebis(2,6-dimethylphenylcyanate), 4, 4′-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate-3,5- Difunctional cyanate resins such as dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether, Polyfunctional cyanate resins derived from phenol novolak, cresol novolak, etc., and prepolymers obtained by partially triazine-forming these cyanate resins. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins), "BA230" and "BA230S75" (part of bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. or a prepolymer that is entirely triazined to form a trimer), and the like.

Specific examples of carbodiimide curing agents include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd., and the like.

When the resin composition contains (D) a curing agent, the amount ratio of (A) epoxy resin and (D) curing agent is [total number of epoxy groups in (A) epoxy resin]:[(D) curing agent total number of reactive groups] is preferably in the range of 1:0.2 to 1:2, more preferably 1:0.3 to 1:1.5, and 1:0.4 to 1:1. 2 is more preferred. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group, or the like, and varies depending on the type of curing agent.

When the (D) curing agent contains an active ester curing agent, the content is not particularly limited, but when the total amount of the (D) curing agent is 100% by mass, it is preferably 10% by mass. Above, more preferably 40% by mass or more, still more preferably 60% by mass or more, and particularly preferably 70% by mass or more. The upper limit of the content of the active ester curing agent is not particularly limited. 85% by mass or less, 80% by mass or less, or the like.

When the resin composition contains (D) a curing agent, its content is not particularly limited. , preferably 1% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and particularly preferably 30% by mass or more. The upper limit of the content of (D) the curing agent is not particularly limited, but when the non-volatile components excluding the (B) inorganic filler in the resin composition is 100% by mass, it is preferably 80% by mass or less. , more preferably 70% by mass or less, still more preferably 60% by mass or less, and particularly preferably 50% by mass or less.

<(E) Curing accelerator>
The resin composition of the present invention may contain (E) a curing accelerator as an optional component. (E) The curing accelerator has a function of accelerating the curing of (A) the epoxy resin.

(E) The curing accelerator is not particularly limited, but for example, phosphorus-based curing accelerator, urea-based curing accelerator, amine-based curing accelerator, imidazole-based curing accelerator, guanidine-based curing accelerator, A metal-based curing accelerator and the like are included. Among them, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are preferable, and amine-based curing accelerators are more preferable. The curing accelerator may be used singly or in combination of two or more.

Phosphorus curing accelerators include, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hydro Aliphatic phosphonium salts such as genhexahydrophthalate, tetrabutylphosphonium cresol novolac trimer salt, di-tert-butylmethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, Butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium Tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphoniumthiocyanate, butyltriphenylphosphonium Aromatic phosphonium salts such as thiocyanate; Aromatic phosphine/borane complexes such as triphenylphosphine/triphenylborane; Aliphatic phosphines such as -tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, tricyclohexylphosphine; dibutylphenylphosphine , di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, Tris(4-ethylphenyl)phosphine, Tris(4-propylphenyl)phosphine, Tris(4-isopropylphenyl)phosphine, Tris(4-butylphenyl)phosphine, Tris(4-tert-butylphenyl)phosphine, Tris(2 ,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethyl phenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4- tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, aromatic phosphines such as 1,2-bis(diphenylphosphino)acetylene and 2,2'-bis(diphenylphosphino)diphenyl ether;

Urea-based curing accelerators include, for example, 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3- Aliphatic dimethylurea such as cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl )-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4- methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4- methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3- [4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene) Aromatic dimethylurea such as bis(N',N'-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea] etc.

Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1, 8-diazabicyclo(5,4,0)-undecene, etc., and 4-dimethylaminopyridine is preferred.

Examples of imidazole curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4- Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate, 2-phenylimidazole isocyanurate, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-phenylimidazoline and other imidazole compounds, and adducts of imidazole compounds and epoxy resins.

As the imidazole-based curing accelerator, a commercially available product may be used, such as "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Guanidine curing accelerators include, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, Pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide and the like.

Metal-based curing accelerators include, for example, organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organocopper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. and the like, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

When the resin composition contains (E) a curing accelerator, the content is not particularly limited, but the non-volatile components excluding the (B) inorganic filler in the resin composition were set to 100% by mass. is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more. (E) The upper limit of the content of the curing accelerator is not particularly limited, but when the non-volatile component excluding the (B) inorganic filler in the resin composition is 100% by mass, it is preferably 5% by mass. Below, more preferably 1% by mass or less, still more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less.

<(F) Flame retardant>
The resin composition of the present invention may contain (F) a flame retardant as an optional component. (F) Flame retardants include phosphorus-based flame retardants such as phosphazene compounds, phosphate esters, and phosphinates; nitrogen-based flame retardants such as aliphatic amine compounds, aromatic amine compounds, nitrogen-containing heterocyclic compounds, and urea compounds; Inorganic flame retardants such as antimony trioxide, antimony pentoxide, sodium antimonate; brominated polycarbonate resin, brominated epoxy resin, brominated phenoxy resin, brominated polyphenylene ether resin, brominated polystyrene resin, brominated benzyl polyacrylate resin and halogen-based flame retardants such as Among them, phosphorus-based flame retardants are preferred. (F) A flame retardant may be used individually by 1 type, or 2 or more types may be used together.

(F) Specific examples of flame retardants include "SPH-100", "SPS-100", "SPB-100" and "SPE-100" (phosphazene compounds) manufactured by Otsuka Chemical; "FP-100", "FP-110", "FP-300", "FP-400" (phosphazene compounds); "HCA-HQ" (phosphate ester) manufactured by Sanko; manufactured by Daihachi Chemical Industry Co., Ltd. "PX-200", "PX-201", "PX-202", "CR-733S", "CR-741", "CR-747" (phosphate ester) and the like.

When the resin composition contains (F) a flame retardant, its content is not particularly limited. , preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more. Although the upper limit of the content of the flame retardant (F) is not particularly limited, it is preferably 30% by mass or less when the non-volatile components excluding the (B) inorganic filler in the resin composition are 100% by mass. , more preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably 3% by mass or less.

<(G) Thermoplastic resin>
The resin composition of the present invention may contain (G) a thermoplastic resin as an optional component. The thermoplastic resin (G) here is a thermoplastic resin that does not correspond to the component (C).

(G) Thermoplastic resins include, for example, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, and polyetheretherketone resins. , polyester resins, etc., and phenoxy resins are preferred. (G) Component may be used individually by 1 type, or may be used in combination of 2 or more type.

(G) The polystyrene equivalent weight average molecular weight of the thermoplastic resin is preferably 2,000 or more, more preferably 5,000 or more, and still more preferably 10,000 or more. The upper limit is preferably 100,000 or less, more preferably 70,000 or less, even more preferably 50,000 or less.

(G) The polystyrene equivalent weight average molecular weight of the component is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-equivalent weight average molecular weight of the component (G) is measured by LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P/K-804L/K manufactured by Showa Denko Co., Ltd. as a column. −804L can be calculated by using chloroform or the like as a mobile phase, measuring the column temperature at 40° C., and using a standard polystyrene calibration curve.

Examples of phenoxy resins include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, and terpene. A phenoxy resin having one or more skeletons selected from the group consisting of a skeleton and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. Specific examples of phenoxy resins include Mitsubishi Chemical's "1256" and "4250" (both phenoxy resins containing bisphenol A skeleton), "YX8100" (phenoxy resin containing bisphenol S skeleton), and "YX6954" (bisphenolacetophenone). Skeleton-containing phenoxy resin), and in addition, "FX280" and "FX293" manufactured by Nippon Steel Chemical & Materials Co., Ltd., "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30" manufactured by Mitsubishi Chemical Corporation, Examples include "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482".

Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, and polyvinyl butyral resins are preferred. Specific examples of polyvinyl acetal resins include Denka Butyral 4000-2, Denka Butyral 5000-A, Denka Butyral 6000-C, Denka Butyral 6000-EP, and Sekisui. S-lec BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, BM series manufactured by Kagaku Kogyo Co., Ltd. may be mentioned.

Specific examples of the polyimide resin include "Ricacoat SN20" and "Ricacoat PN20" manufactured by Shin Nippon Rika. Specific examples of polyimide resins also include linear polyimides obtained by reacting bifunctional hydroxyl group-terminated polybutadiene, diisocyanate compounds and tetrabasic acid anhydrides (polyimides described in JP-A-2006-37083), and polysiloxane skeletons. Examples include modified polyimides such as polyimide containing (polyimides described in JP-A-2002-12667 and JP-A-2000-319386).

Specific examples of polyamide-imide resins include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamideimide resins include modified polyamideimides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamideimides) manufactured by Hitachi Chemical Co., Ltd.

Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like. Specific examples of the polyphenylene ether resin include oligophenylene ether/styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Company, Inc., and the like. Specific examples of the polyetheretherketone resin include "Sumiproy K" manufactured by Sumitomo Chemical Co., Ltd., and the like. Specific examples of the polyetherimide resin include "Ultem" manufactured by GE.

Specific examples of the polysulfone resin include polysulfone "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

Examples of polyolefin resins include ethylene-based copolymers such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer. Resin etc. are mentioned.

Examples of polyester resins include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, polycyclohexanedimethyl terephthalate resin, and the like.

When the resin composition contains (G) a thermoplastic resin, the content is not particularly limited, but the non-volatile components excluding the (B) inorganic filler in the resin composition were set to 100% by mass. is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more. (G) The upper limit of the content of the thermoplastic resin is not particularly limited, but when the non-volatile components excluding the (B) inorganic filler in the resin composition are 100% by mass, it is preferably 30% by mass. Below, more preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably 3% by mass or less.

<(H) Other Additives>
The resin composition of the present invention may further contain optional additives as non-volatile components. Examples of such additives include organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; Colorants; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as siloxane; thickeners such as bentone and montmorillonite; Antifoaming agents for resin-based antifoaming agents; UV absorbers such as benzotriazole-based UV absorbers; Adhesion improvers such as urea silane; Adhesion-imparting agents such as triazine-based adhesion-imparting agents; antioxidants such as hindered phenol-based antioxidants and hindered amine-based antioxidants; fluorescent brighteners such as stilbene derivatives; fluorine-based surfactants and silicone-based interfaces Examples thereof include surfactants such as active agents. One of the additives may be used alone, or two or more of them may be used in combination at an arbitrary ratio. (H) The content of other additives can be appropriately set by those skilled in the art.

<(I) Organic solvent>
The resin composition of the present invention may further contain an arbitrary organic solvent as a volatile component in addition to the non-volatile component described above. (I) As the organic solvent, a known solvent can be used as appropriate, and the type is not particularly limited. (I) Examples of organic solvents include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, and diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; Ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, methyl methoxypropionate; methyl lactate, ethyl lactate, 2-hydroxyisobutyric acid ester alcohol solvents such as methyl; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol); N,N-dimethylformamide, Amide solvents such as N,N-dimethylacetamide and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethylsulfoxide; nitrile solvents such as acetonitrile and propionitrile; hexane, cyclopentane, cyclohexane, methylcyclohexane and the like Aliphatic hydrocarbon solvents; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, and the like can be mentioned. (I) The organic solvent may be used singly or in combination of two or more at any ratio. (I) The content of the organic solvent can be appropriately set by those skilled in the art.

<Method for producing resin composition>
The resin composition of the present invention is, for example, placed in an arbitrary reaction vessel (A) an epoxy resin, (B) an inorganic filler, (C) a particulate or non-particulate elastomer, optionally (D) a curing agent, Optionally (E) curing accelerator, optionally (F) flame retardant, optionally (G) thermoplastic resin, optionally (H) other additives, and optionally ( I) can be produced by adding and mixing organic solvents in any order and/or partly or wholly at the same time. Also, during the process of adding and mixing each component, the temperature can be set appropriately, and heating and/or cooling may be performed temporarily or over time. Moreover, you may stir or shake in the process of adding and mixing each component. In addition, during or after the addition and mixing, the resin composition may be stirred using a stirring device such as a mixer to uniformly disperse.

<Characteristics of resin composition>
The resin composition of the present invention contains (A) an epoxy resin, (B) an inorganic filler, and (C) a particulate or non-particulate elastomer, and component (B) has a specific surface area of 10 m ² /g or more. The content of component (C) is 35% by mass or less (ratio of components excluding component (B)), and the average particle size of component (C) is 0.8 μm or less, so warping of the cured product is suppressed. In addition, excellent insulation reliability, adhesion, and small-diameter via formability can be achieved.

Since the resin composition of the present invention can suppress warping of the cured product, for example, the thickness of the resin composition when pressed on one side of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 3 μm, substrate thickness 0.15 mm) When a resin composition layer having a thickness of 15 μm and 14 cm square is cured at 190° C. for 90 minutes, the warp is preferably less than 3 cm, more preferably less than 2 cm, and particularly preferably less than 1 cm.

Since the cured product of the resin composition of the present invention has excellent insulation reliability, the resistance value measured under the conditions of Test Example 1 below is preferably 1.0×10 ¹⁰ Ω or more, more preferably 1.0×10 10 Ω or more. 0×10 ⁷ Ω or more, more preferably 1.0×10 ⁶ Ω or more, and particularly preferably 1.0×10 ⁵ Ω or more.

Since the cured product of the resin composition of the present invention has excellent adhesiveness, the resin composition was pressed against the roughened surface of the copper foil (Ra value = 1 µm) at 100 ° C. and 0.74 MPa for 30 seconds. After curing the material layer at 190 ° C. for 90 minutes to form a cured material layer, the peel strength when the copper foil is peeled off vertically from the cured material layer at a speed of 50 mm / min (copper foil peel strength before HAST ) is preferably 0.50 kgf/cm or more, more preferably 0.55 kgf/cm or more, still more preferably 0.60 kgf/cm or more, and particularly preferably 0.65 kgf/cm or more.

Further, the resin composition layer was pressed against the roughened surface (Ra value = 1 µm) of the copper foil at 100 ° C. and 0.74 MPa for 30 seconds and cured at 190 ° C. for 90 minutes to form a cured product layer. ° C., 85% relative humidity, and 3.3 V DC voltage applied for 200 hours, and then the peel strength (after HAST copper foil peel strength) is preferably 0.20 kgf/cm or more, more preferably 0.30 kgf/cm or more, still more preferably 0.35 kgf/cm or more, and particularly preferably 0.40 kgf/cm or more.

In addition, the cured product layer obtained by curing the resin composition of the present invention under the curing conditions of 130° C. for 30 minutes and 170° C. for 30 minutes was roughened under the conditions of Test Example 4 below, and the thickness was 20 μm by a semi-additive method. After forming the conductor layer, the peel strength (plating peel strength) when the conductor layer is peeled off from the cured product layer by 35 mm in the vertical direction at a speed of 50 mm / min is preferably 0.20 kgf / cm or more, more It is preferably 0.30 kgf/cm or more, more preferably 0.40 kgf/cm or more, and particularly preferably 0.45 kgf/cm or more.

Since the cured product of the resin composition of the present invention has excellent small-diameter via formation properties, the ratio of the top area to the bottom area of the via hole after roughening treatment formed in the cured product layer under the conditions of Test Example 5 below (Bottom area/top area) can be preferably 50% or more, particularly preferably 60% or more. The upper limit of the ratio of the top area to the bottom area is not particularly limited, but may be, for example, 100%, 98%, 95%, 90%.

<Application of resin composition>
The resin composition of the present invention can be suitably used as a resin composition for insulation, particularly as a resin composition for forming an insulation layer. Specifically, a resin composition for forming an insulating layer for forming a conductor layer (including a rewiring layer) formed on an insulating layer (resin for forming an insulating layer for forming a conductor layer composition). Moreover, in the printed wiring board described later, it can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for forming an insulating layer of a printed wiring board). The resin composition of the present invention also includes resin sheets, sheet laminate materials such as prepreg, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, component-embedding resins, and the like. It can be used in a wide range of applications.

Further, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention is used as an insulating layer for forming a rewiring layer. (a resin composition for forming a rewiring layer) and a resin composition for sealing a semiconductor chip (a resin composition for semiconductor chip sealing). A rewiring layer may be further formed on the encapsulation layer when the semiconductor chip package is manufactured.
(1) a step of laminating a temporary fixing film on a substrate;
(2) temporarily fixing the semiconductor chip on the temporary fixing film;
(3) forming a sealing layer on the semiconductor chip;
(4) a step of peeling the substrate and the temporary fixing film from the semiconductor chip;
(5) Forming a rewiring layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been removed; and (6) Forming a rewiring layer as a conductor layer on the rewiring layer. forming process

Moreover, since the resin composition of the present invention provides an insulating layer having good component embedding properties, it can be suitably used when the printed wiring board is a component built-in circuit board.

<Sheet-like laminated material>
Although the resin composition of the present invention can be applied in the form of a varnish, it is industrially preferably used in the form of a sheet-like laminated material containing the resin composition.

As the sheet-like laminate material, resin sheets and prepregs shown below are preferable.

In one embodiment, the resin sheet comprises a support and a resin composition layer provided on the support, and the resin composition layer is formed from the resin composition of the present invention.

The thickness of the resin composition layer is preferably 50 μm or less, more It is preferably 40 μm or less. Although the lower limit of the thickness of the resin composition layer is not particularly limited, it can be usually 5 μm or more, 10 μm or more, or the like.

Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"). ), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketones, polyimides, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. may be used.

The support may be subjected to matte treatment, corona treatment, or antistatic treatment on the surface to be bonded to the resin composition layer.

Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. The release agent used in the release layer of the release layer-attached support includes, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used, for example, "SK-1", " AL-5", "AL-7", Toray's "Lumirror T60", Teijin's "Purex", and Unitika's "Unipeel".

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When a release layer-attached support is used, the thickness of the release layer-attached support as a whole is preferably within the above range.

In one embodiment, the resin sheet may further contain any layer as necessary. Examples of such an optional layer include a protective film conforming to the support provided on the surface of the resin composition layer not bonded to the support (that is, the surface opposite to the support). be done. Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. By laminating the protective film, the surface of the resin composition layer can be prevented from being dusted or scratched.

For the resin sheet, for example, a liquid resin composition is used as it is, or a resin varnish is prepared by dissolving the resin composition in an organic solvent. It can be produced by allowing the resin composition layer to form.

Examples of the organic solvent include the same organic solvents as those described as components of the resin composition. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

Drying may be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Depending on the boiling point of the organic solvent in the resin composition or resin varnish, for example, when using a resin composition or resin varnish containing 30% by mass to 60% by mass of the organic solvent, the temperature is 50° C. to 150° C. for 3 minutes to 10 minutes. A resin composition layer can be formed by drying for minutes.

The resin sheet can be wound into a roll and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

In one embodiment, the prepreg is formed by impregnating a sheet-like fiber base material with the resin composition of the present invention.

The sheet-like fiber base material used for the prepreg is not particularly limited, and those commonly used as base materials for prepreg, such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric, can be used. From the viewpoint of thinning the printed wiring board, the thickness of the sheet-like fiber base material is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber base material is not particularly limited. Usually, it is 10 μm or more.

A prepreg can be manufactured by a known method such as a hot melt method or a solvent method.

The thickness of the prepreg can be in the same range as the resin composition layer in the resin sheet described above.

The sheet-like laminated material of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and for forming an interlayer insulating layer of a printed wiring board (for a printed wiring board). for interlayer insulating layers of wiring boards).

<Printed wiring board>
The printed wiring board of the present invention includes an insulating layer made of a cured product obtained by curing the resin composition of the present invention.

A printed wiring board can be manufactured, for example, using the resin sheet described above by a method including the following steps (I) and (II).
(I) A step of laminating a resin sheet on the inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate (II) Curing (for example, thermosetting) the resin composition layer to form an insulating layer process

The "inner layer substrate" used in step (I) is a member that serves as a printed wiring board substrate, and includes, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. etc. The substrate may also have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner layer substrate having conductor layers (circuits) formed on one side or both sides of the substrate is sometimes referred to as an "inner layer circuit board." Further, an intermediate product on which an insulating layer and/or a conductor layer are to be further formed when manufacturing a printed wiring board is also included in the "inner layer board" as used in the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components may be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "thermocompression bonding member") include heated metal plates (such as SUS end plates) and metal rolls (SUS rolls). Instead of pressing the thermocompression member directly onto the resin sheet, it is preferable to press through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the uneven surface of the inner layer substrate.

Lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60° C. to 160° C., more preferably 80° C. to 140° C., and the thermocompression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. .29 MPa to 1.47 MPa, and the heat pressing time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination can be carried out under reduced pressure conditions, preferably at a pressure of 26.7 hPa or less.

Lamination can be done with a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, a batch-type vacuum pressurized laminator, and the like.

After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. Pressing conditions for the smoothing treatment may be the same as the thermocompression bonding conditions for the lamination described above. Smoothing treatment can be performed with a commercially available laminator. Lamination and smoothing may be performed continuously using the above-mentioned commercially available vacuum laminator.

The support may be removed between steps (I) and (II) or after step (II).

In step (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer made of the cured resin composition. Curing conditions for the resin composition layer are not particularly limited, and conditions that are usually employed when forming an insulating layer of a printed wiring board may be used.

For example, although the thermosetting conditions for the resin composition layer vary depending on the type of resin composition, etc., the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and still more preferably 170°C to 210°C. °C. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, even more preferably 15 minutes to 100 minutes.

Before thermosetting the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is cured at a temperature of 50° C. to 120° C., preferably 60° C. to 115° C., more preferably 70° C. to 110° C. for 5 minutes or more, It may be preheated for preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, even more preferably 15 minutes to 100 minutes.

When manufacturing a printed wiring board, (III) the step of drilling holes in the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming a conductor layer may be further carried out. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art that are used in the manufacture of printed wiring boards. When the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or step ( It may be carried out between IV) and step (V). If necessary, the steps (II) to (V) of forming the insulating layer and the conductor layer may be repeated to form a multilayer wiring board.

In another embodiment, the printed wiring board of the present invention can be manufactured using the prepreg described above. The manufacturing method is basically the same as in the case of using a resin sheet.

Step (III) is a step of making holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be performed using, for example, a drill, laser, plasma, or the like, depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be appropriately determined according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. Smear is usually also removed in this step (IV). The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are commonly used in forming insulating layers of printed wiring boards can be employed. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing liquid in this order.

The swelling liquid used for the roughening treatment is not particularly limited, but examples thereof include alkaline solutions, surfactant solutions, etc., preferably alkaline solutions, more preferably sodium hydroxide solutions and potassium hydroxide solutions. preferable. Examples of commercially available swelling liquids include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU" manufactured by Atotech Japan. The swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in the swelling liquid at 30.degree. C. to 90.degree. C. for 1 to 20 minutes. From the viewpoint of suppressing swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40° C. to 80° C. for 5 minutes to 15 minutes.

The oxidizing agent used in the roughening treatment is not particularly limited, but examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60° C. to 100° C. for 10 to 30 minutes. Further, the permanganate concentration in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan.

Moreover, as a neutralization liquid used for the roughening treatment, an acidic aqueous solution is preferable, and as a commercial product, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan Co., Ltd. can be mentioned.

The treatment with the neutralizing solution can be carried out by immersing the treated surface roughened with the oxidizing agent in the neutralizing solution at 30° C. to 80° C. for 5 to 30 minutes. From the viewpoint of workability, etc., a method of immersing an object roughened with an oxidizing agent in a neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes is preferable.

In one embodiment, the arithmetic mean roughness (Ra) of the insulating layer surface after roughening treatment is not particularly limited, but is preferably 500 nm or less, more preferably 400 nm or less, and still more preferably 300 nm or less. . The lower limit is not particularly limited, and may be, for example, 1 nm or more, 2 nm or more. The root mean square roughness (Rq) of the surface of the insulating layer after roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less. The lower limit is not particularly limited, and may be, for example, 1 nm or more, 2 nm or more. The arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

Step (V) is a step of forming a conductor layer, in which the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, a nickel-chromium alloy, a copper- nickel alloys and copper-titanium alloys). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, nickel-chromium alloys, copper- Nickel alloys and copper/titanium alloy alloy layers are preferred, and single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel/chromium alloy alloy layers are more preferred, and copper single metal layers are preferred. A metal layer is more preferred.

The conductor layer may have a single layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different kinds of metals or alloys are laminated. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.

The thickness of the conductor layer is generally between 3 μm and 35 μm, preferably between 5 μm and 30 μm, depending on the desired printed wiring board design.

In one embodiment, the conductor layer may be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating the surface of an insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. It is preferably formed by a method. An example of forming a conductor layer by a semi-additive method is shown below.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a portion of the plating seed layer corresponding to a desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electroplating, the mask pattern is removed. After that, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

In other embodiments, the conductor layer may be formed using a metal foil. When forming the conductor layer using a metal foil, step (V) is preferably performed between step (I) and step (II). For example, after step (I), the support is removed and a metal foil is laminated on the exposed surface of the resin composition layer. Lamination of the resin composition layer and the metal foil may be carried out by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Then, step (II) is performed to form an insulating layer. After that, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by conventional known techniques such as the subtractive method and the modified semi-additive method.

A metal foil can be manufactured by a known method such as an electrolysis method or a rolling method. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Co., Ltd., 3EC-III foil and TP-III foil manufactured by Mitsui Kinzoku Mining Co., Ltd., and the like.

<Semiconductor device>
A semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

Examples of semiconductor devices include various semiconductor devices used in electrical appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.).

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. The invention is not limited to these examples. In the following, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

<Measurement of average particle size of inorganic filler>
100 mg of an inorganic filler, 0.1 g of a dispersant (“SN9228” manufactured by San Nopco), and 10 g of methyl ethyl ketone were weighed into a vial and dispersed by ultrasonic waves for 20 minutes. Using a laser diffraction particle size distribution analyzer ("SALD-2200" manufactured by Shimadzu Corporation), the particle size distribution was measured by a batch cell method, and the average particle size was calculated from the median diameter.

<Measurement of average particle size of rubber particles>
The average particle size of rubber particles can be measured using a dynamic light scattering method. Specifically, the rubber particles are uniformly dispersed in an appropriate organic solvent by a method such as ultrasonic waves, and the particle size distribution of the rubber particles is analyzed using a concentrated particle size analyzer (“FPAR-1000” manufactured by Otsuka Electronics Co., Ltd.). is created on the basis of mass,
The median diameter was measured as the average particle diameter.

<Synthesis Example 1>
A reaction vessel was charged with 69 g of bifunctional hydroxy-terminated polybutadiene (G-1000, manufactured by Nippon Soda Co., Ltd., number average molecular weight = 1,000, hydroxy group equivalent = 1,800 g/eq.), and Ipsol 150 (aromatic hydrocarbon-based Mixed solvent: 40 g of Idemitsu Petrochemical Co., Ltd.) and 0.005 g of dibutyltin laurate were mixed and uniformly dissolved. When the mixture became uniform, the temperature was raised to 50° C., and while stirring, 8 g of isophorone diisocyanate (IPDI, isocyanate group equivalent=113 g/eq., manufactured by Evonik Degussa Japan) was added and reacted for about 3 hours. Next, after cooling the reactant to room temperature, 23 g of cresol novolak resin (KA-1160, manufactured by DIC, hydroxyl group equivalent = 117 g/eq.) and 60 g of ethyl diglycol acetate (manufactured by Daicel) were added. Then, the temperature was raised to 80° C. while stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak at 2250 cm ⁻¹ was confirmed by FT-IR. Confirmation of the disappearance of the NCO peak was regarded as the end point of the reaction, and the reaction product was cooled to room temperature and filtered through a 100-mesh filter cloth to obtain a liquid phenolic hydroxyl group-containing polybutadiene resin (50% by mass of nonvolatile matter). The number average molecular weight was 4,500.

<Synthesis Example 2>
A reaction vessel was charged with 69 g of bifunctional hydroxy-terminated polybutadiene (G-2000, manufactured by Nippon Soda Co., Ltd., number average molecular weight = 3,000, hydroxy group equivalent = 1,800 g/eq.) and Ipsol 150 (aromatic hydrocarbon-based Mixed solvent: 40 g of Idemitsu Petrochemical Co., Ltd.) and 0.005 g of dibutyltin laurate were mixed and uniformly dissolved. When the mixture became uniform, the temperature was raised to 50° C., and while stirring, 8 g of isophorone diisocyanate (IPDI, isocyanate group equivalent=113 g/eq., manufactured by Evonik Degussa Japan) was added and reacted for about 3 hours. Next, after cooling the reactant to room temperature, 23 g of cresol novolak resin (KA-1160, manufactured by DIC, hydroxyl group equivalent = 117 g/eq.) and 60 g of ethyl diglycol acetate (manufactured by Daicel) were added. Then, the temperature was raised to 80° C. while stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak at 2250 cm ⁻¹ was confirmed by FT-IR. Confirmation of the disappearance of the NCO peak was regarded as the end point of the reaction, and the reaction product was cooled to room temperature and filtered through a 100-mesh filter cloth to obtain a liquid phenolic hydroxyl group-containing polybutadiene resin (50% by mass of nonvolatile matter). The number average molecular weight was 5,500.

<Example 1>
10 parts of bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation "828US", epoxy equivalent of about 180 g / eq.), naphthalene type epoxy resin (DIC Corporation "HP-4032SS", epoxy equivalent of about 140 g / eq.) 10 parts, 20 parts of biphenyl-type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269 g/eq.), 20 parts of biphenyl-type epoxy resin ("YX4000H" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 190 g/eq.), phosphazene Resin ("PX-200" manufactured by Otsuka Chemical Co., Ltd.) 3 parts, phenoxy resin (manufactured by Mitsubishi Chemical Corporation "YX7553BH30", 1: 1 solution of MEK and cyclohexanone with a solid content of 30% by mass) 10 parts, urethane rubber particles (Negami Kogyo "MM-101SM" manufactured by Co., Ltd., average particle size 0.07 to 0.10 μm, solid content 30% by mass, 4:1 solution of MEK and cyclohexane) was dissolved in 60 parts of MEK by heating with stirring.

After cooling to room temperature, active ester curing agent (manufactured by DIC "HPC-8000-65T", active group equivalent of about 223 g / eq., solid content of 65% by weight toluene solution) 70 parts, phenolic curing agent ( DIC's "LA-3018-50P", active group equivalent of about 151 g / eq., 2-methoxypropanol solution with a solid content of 50%) 6 parts, carbodiimide curing agent (Nisshinbo Chemical Co., Ltd. "V-03", active Base equivalent about 216 g / eq., solid content 50 wt% toluene solution) 18 parts, curing accelerator (4-dimethylaminopyridine (DMAP), solid content 5 wt% MEK solution) 6 parts, N-phenyl-8 - Spherical silica (“UFP-20” manufactured by Denka, specific surface area 22 m ² /g, average particle size 0.15 μm) surface-treated with aminooctyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 325.2) 300 The parts were mixed, dispersed uniformly with a high-speed rotating mixer, and then filtered through a cartridge filter ("SHP020" manufactured by ROKITECHNO) to prepare a resin composition.

<Example 2>
Urethane rubber particles ("MM-101SM" manufactured by Negami Kogyo Co., Ltd., average particle size 0.07 to 0.10 μm, 4: 1 solution of MEK and cyclohexane with a solid content of 30% by mass) 28 parts of liquid epoxy group-containing polybutadiene resin ( A resin composition was prepared in the same manner as in Example 1, except that "JP-100" manufactured by Nippon Soda Co., Ltd. (epoxy equivalent: about 210 g/eq.) was changed to 8.5 parts.

<Example 3>
N-phenyl-8-aminooctyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 325.2) surface-treated spherical silica (“UFP-20” manufactured by Denka Co., Ltd., specific surface area 22 m / g, average particle diameter 0 A resin composition was prepared in the same manner as in Example 1, except that 300 parts of .15 μm) was changed to 110 parts.

<Example 4>
28 parts of urethane rubber particles ("MM-101SM" manufactured by Neagari Kogyo Co., Ltd., average particle size 0.07 to 0.10 μm, 4:1 solution of MEK and cyclohexane with a solid content of 30% by mass) were added to the liquid obtained in Synthesis Example 1. A resin composition was prepared in the same manner as in Example 1, except that 17 parts of a phenolic hydroxyl group-containing polybutadiene resin (solid content: 50%, number average molecular weight: 4,500) was used.

<Example 5>
28 parts of urethane rubber particles (“MM-101SM” manufactured by Negami Kogyo Co., Ltd., average particle size 0.07 to 0.10 μm, 4:1 solution of MEK and cyclohexane with a solid content of 30% by mass) obtained in Synthesis Example 2 A resin composition was prepared in the same manner as in Example 1, except that 17 parts of a phenolic hydroxyl group-containing polybutadiene resin (solid content: 50%, number average molecular weight: 5,500) was used.

<Example 6>
28 parts of urethane rubber particles ("MM-101SM" manufactured by Neagari Kogyo Co., Ltd., average particle size 0.07 to 0.10 μm, 4:1 solution of MEK and cyclohexane with a solid content of 30% by mass) were added to the liquid obtained in Synthesis Example 1. A resin composition was prepared in the same manner as in Example 1, except that 80 parts of a phenolic hydroxyl group-containing polybutadiene resin (solid content: 50%, number average molecular weight: 4,500) was used.

<Example 7>
Urethane rubber particles ("MM-101SM" manufactured by Negami Kogyo Co., Ltd., average particle size 0.07 to 0.10 μm, 4: 1 solution of MEK and cyclohexane with a solid content of 30% by mass) 28 parts of liquid epoxy group-containing polybutadiene resin ( "JP-100" manufactured by Nippon Soda Co., Ltd., epoxy equivalent of about 210 g / eq.) Changed to 8.5 parts, active ester curing agent (DIC "HPC-8000-65T", active group equivalent of about 223 g / eq. ., a toluene solution with a solid content of 65% by mass) 70 parts of an active ester curing agent ("HPC-8150-60T" manufactured by DIC, active group equivalent of about 220 g / eq., a toluene solution with a solid content of 60% by mass) 65 A resin composition was prepared in the same manner as in Example 1, except that parts were changed.

<Comparative Example 1>
Urethane rubber particles (manufactured by Negami Kogyo Co., Ltd. "MM-101SM", average particle size 0.07 to 0.10 μm, 4: 1 solution of MEK and cyclohexane with a solid content of 30% by mass) 28 parts of rubber particles (manufactured by Negami Kogyo Co., Ltd. "MM-110SM", average particle size 1 μm, 4:1 solution of MEK and cyclohexanone with a solid content of 30% by mass) 28 parts, N-phenyl-8-aminooctyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., 300 parts of spherical silica (“UFP-20” manufactured by Denka, specific surface area 22 m ² /g, average particle diameter 0.15 μm) surface-treated with N-phenyl-8-aminooctyltrimethoxysilane (molecular weight 325.2). (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 325.2) surface-treated spherical silica (“SC2050-SXF” manufactured by Admatechs, specific surface area 5.9 m ² /g, average particle size 0.77 μm) changed to 300 parts A resin composition was prepared in the same manner as in Example 1, except that

<Comparative Example 2>
N-phenyl-8-aminooctyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 325.2) spherical silica (“UFP-20” manufactured by Denka Co., Ltd., specific surface area 22 m ² /g, average particle size 0.15 μm) was treated with 300 parts of N-phenyl-8-aminooctyl-trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 325.2). A resin composition was prepared in the same manner as in Example 1, except that the surface area was 5.9 m ² /g and the average particle diameter was 0.77 μm) (300 parts).

<Comparative Example 3>
Urethane rubber particles (manufactured by Negami Kogyo Co., Ltd. "MM-101SM", average particle size 0.07 to 0.10 μm, 4: 1 solution of MEK and cyclohexane with a solid content of 30% by mass) 28 parts of rubber particles (manufactured by Negami Kogyo Co., Ltd. A resin composition was prepared in the same manner as in Example 1, except that "MM-110SM", an average particle size of 1 μm, a 4:1 solution of MEK and cyclohexanone having a solid content of 30% by mass) was changed to 28 parts.

<Comparative Example 4>
Urethane rubber particles (“MM-101SM” manufactured by Negami Kogyo Co., Ltd., average particle size 0.07 to 0.10 μm, 4:1 solution of MEK and cyclohexane with a solid content of 30% by mass) 28 parts were not used. A resin composition was prepared in the same manner as in Example 1.

<Comparative Example 5>
In Example 1, 28 parts of urethane rubber particles ("MM-101SM" manufactured by Negami Kogyo Co., Ltd., average particle size 0.07 to 0.10 μm, 4:1 solution of MEK and cyclohexane with a solid content of 30% by mass) were synthesized. A resin composition was prepared in the same manner as in Example 1, except that the liquid phenolic hydroxyl group-containing polybutadiene resin obtained in 1 (solid content: 50%, number average molecular weight: 4,500) was changed to 160 parts.

<Production Example 1: Production of resin sheet A>
As a support, a PET film (“Lumirror R80” manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130 ° C., hereinafter “release PET” released with an alkyd resin release agent (“AL-5” manufactured by Lintec Co., Ltd.) There is a thing called.) was prepared.

Each resin composition prepared in Examples or Comparative Examples is uniformly applied on a release PET with a die coater so that the thickness of the resin composition layer after drying is 6 μm, and dried at 80 ° C. for 1 minute. Thus, a resin composition layer was obtained on the release PET. Next, on the surface of the resin composition layer that is not bonded to the support, a rough surface of a polypropylene film (manufactured by Oji F-Tex Co., Ltd. "Alphan MA-411", thickness 15 μm) as a protective film is bonded to the resin composition layer. It was laminated so as to As a result, a “resin sheet A” consisting of the release PET (support), the resin composition layer, and the protective film was produced.

<Production Example 2: Production of resin sheet B>
As a support, a PET film (“Lumirror R80” manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130 ° C., hereinafter “release PET” released with an alkyd resin release agent (“AL-5” manufactured by Lintec Co., Ltd.) There is a thing called.) was prepared.

Each resin composition prepared in Examples or Comparative Examples is uniformly applied on a release PET with a die coater so that the thickness of the resin composition layer after drying is 10 μm, and dried at 80 ° C. for 2 minutes. Thus, a resin composition layer was obtained on the release PET. Next, on the surface of the resin composition layer that is not bonded to the support, a rough surface of a polypropylene film (manufactured by Oji F-Tex Co., Ltd. "Alphan MA-411", thickness 15 μm) as a protective film is bonded to the resin composition layer. It was laminated so as to As a result, a “resin sheet B” consisting of the release PET (support), the resin composition layer, and the protective film was produced.

<Production Example 3: Production of resin sheet C>
As a support, a PET film (“Lumirror R80” manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130 ° C., hereinafter “release PET” released with an alkyd resin release agent (“AL-5” manufactured by Lintec Co., Ltd.) There is a thing called.) was prepared.

Each resin composition prepared in Examples or Comparative Examples is uniformly applied on a release PET with a die coater so that the thickness of the resin composition layer after drying is 15 μm, and dried at 80 ° C. for 2 minutes. Thus, a resin composition layer was obtained on the release PET. Next, on the surface of the resin composition layer that is not bonded to the support, a rough surface of a polypropylene film (manufactured by Oji F-Tex Co., Ltd. "Alphan MA-411", thickness 15 μm) as a protective film is bonded to the resin composition layer. It was laminated so as to As a result, a “resin sheet C” was produced, which consisted of the release PET (support), the resin composition layer, and the protective film in that order.

<Test Example 1: Evaluation of insulation reliability>
(Preparation of substrate for evaluation)
(1) Surface treatment of inner layer circuit board As the inner layer circuit board, glass cloth base epoxy resin both sides having circuit conductors (copper) formed with a wiring pattern of L/S (line/space) = 2 µm/2 µm on both sides A copper-clad laminate (thickness of copper foil: 3 μm, substrate thickness: 0.15 mm, “HL832NSF LCA” manufactured by Mitsubishi Gas Chemical Co., Ltd., size: 255×340 mm) was prepared. Both surfaces of the inner layer circuit board were subjected to an organic coating treatment on the copper surface using "FlatBOND-FT" manufactured by MEC.

(2) Resin sheet lamination The protective film is peeled off from the resin sheet A prepared in Production Example 1, and a batch type vacuum pressure laminator (manufactured by Nikko Materials Co., Ltd., 2-stage build-up laminator, CVP700) is used to obtain a resin composition. Both sides of the inner layer circuit board were laminated so that the material layer was in contact with the inner layer circuit board. Lamination was carried out by pressure bonding for 45 seconds at 130° C. and a pressure of 0.74 MPa after reducing the pressure for 30 seconds to an atmospheric pressure of 13 hPa or less. Then, hot pressing was performed at 120° C. and a pressure of 0.5 MPa for 75 seconds.

(3) Thermosetting of resin composition layer The inner layer circuit board laminated with the resin sheet is placed in an oven at 130°C for 30 minutes, then transferred to an oven at 170°C for 30 minutes, then heat-cured to increase the thickness. An insulating layer of 5 μm was formed, and the release PET was peeled off. This is referred to as "substrate A".

(4) Step of Roughening Treatment The insulating layer of the substrate A was subjected to a desmear treatment as a roughening treatment. As the desmear treatment, the following wet desmear treatment was performed.

Wet desmear treatment:
Swelling liquid ("Swelling Dip Securigant P" manufactured by Atotech Japan Co., Ltd., an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C. for 5 minutes, then an oxidizing agent solution ("Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd.) , an aqueous solution with a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%) at 80 ° C for 10 minutes, and finally a neutralizing solution ("Reduction Solution Securigant P" manufactured by Atotech Japan Co., Ltd., an aqueous sulfuric acid solution). After being immersed at 40°C for 5 minutes, it was dried at 80°C for 15 minutes. This is referred to as "roughened substrate A".

(5) Step of forming a conductor layer (5-1) Electroless plating step In order to form a conductor layer on the surface of the insulating layer of the roughened substrate A, a plating step (Atotech Japan Co., Ltd.) including the following steps 1 to 6 A copper plating process using a chemical solution manufactured by the company) was performed to form a conductor layer.

1. Alkali cleaning (cleaning and charge adjustment of the surface of the insulating layer with via holes)
The surface of the roughened substrate A was cleaned with Cleaning Cleaner Security 902 (trade name) at 60° C. for 5 minutes.
2. Soft etching (cleaning inside via holes)
The surface of the roughened substrate A was treated with a sulfuric acid sodium peroxodisulfate aqueous solution at 30° C. for 1 minute.
3. Pre-dip (adjustment of surface charge of insulating layer for Pd application)
The surface of roughened substrate A was subjected to Pre. Dip Neoganth B (trade name) was used for 1 minute at room temperature.
4. Application of activator (application of Pd to the surface of the insulating layer)
The surface of roughened substrate A was treated with Activator Neoganth 834 (trade name) at 35° C. for 5 minutes.
5. Reduction (reduction of Pd applied to the insulating layer)
The surface of the roughened substrate A was treated with Reducer Neoganth WA (trade name) and Reducer Accelerator 810 mod. (trade name) and treated at 30° C. for 5 minutes.
6. Electroless copper plating process (Cu is deposited on the surface of the insulating layer (Pd surface))
The surface of the roughened substrate A was mixed with Basic Solution Printganth MSK-DK (trade name), Copper solution Printganth MSK (trade name), Stabilizer Printganth MSK-DK (trade name), and Reducer Cu (trade name). The solution was treated at 35° C. for 20 minutes. The thickness of the formed electroless copper plating layer was 0.8 μm.

(5-2) Electroplating Process Next, an electrolytic copper plating process was performed using a chemical solution manufactured by Atotech Japan Co., Ltd. under the condition that the via holes were filled with copper. After that, as a resist pattern for patterning by etching, a land pattern with a diameter of 1 mm connected to the via hole and a circular conductor pattern with a diameter of 10 mm not connected to the lower layer conductor were used to form a 10 μm thick resist pattern on the surface of the insulating layer. Then, a conductor layer having lands and conductor patterns was formed. Annealing was then performed at 200° C. for 90 minutes. This board was used as an "evaluation board".

(Measurement of thickness of insulating layer)
A cross-sectional observation of the substrate for evaluation was performed using an FIB-SEM composite apparatus ("SMI3050SE" manufactured by SII Nano Technology Co., Ltd.). Specifically, a cross section perpendicular to the surface of the conductor layer was cut out by FIB (focused ion beam), and the thickness of the insulating layer between the conductor layers was measured from the cross-sectional SEM image. For each sample, cross-sectional SEM images were observed at five randomly selected locations, and the average value was taken as the insulating layer thickness (μm) between the conductor layers and shown in the table below.

(Measurement of insulation layer resistance)
The circular conductor side with a diameter of 10 mm of the evaluation board obtained above is used as a + electrode, and the lattice conductor (copper) side of the inner layer circuit board connected to the land with a diameter of 1 mm is used as a - electrode. "PM422" manufactured by J-RAS Co., Ltd.), and the insulation resistance value after 200 hours under the conditions of 130 ° C., 85% relative humidity, and 3.3 V DC voltage application is measured by an electrochemical migration tester (manufactured by J-RAS " ECM-100”). This measurement was performed 6 times, and when the resistance value ^of all 6 test pieces was 1.0×10 ⁷ Ω or more, it was marked as “○”. ”, and are shown in the table below together with the evaluation results and insulation resistance values. The resistance minimum value shown in Table 1 below is the minimum insulation resistance value of the six test pieces.

<Test Example 2: Evaluation of warpage>
(1) Lamination of resin composition layer The resin sheet C prepared in Preparation Example 3 was cut into a size of 14 cm square, and a batch type vacuum pressure laminator (manufactured by Nikko Materials, 2-stage build-up laminator, CVP700) was used. A glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 3 μm, substrate thickness 0.15 mm, Mitsubishi Gas Chemical Company “HL832NSF LCA”, 255 × 340 mm size) cut into 15 cm squares. Laminated on one side.
Lamination was carried out by pressure bonding at 120° C. for 30 seconds at a pressure of 0.74 MPa after reducing the pressure for 30 seconds to a pressure of 13 hPa or less to prepare a substrate with a resin composition layer, and then peeling off the PET film.

(2) Curing of the resin composition layer The four sides of the substrate with the resin composition layer obtained in (1) above are attached to a 1 mm thick SUS plate with polyimide tape so that the resin composition layer faces upward, The resin composition layer was cured under curing conditions of 190° C. for 90 minutes.

(3) Measurement of warpage By peeling off the polyimide tape on three sides of the four sides of the substrate with the resin composition layer obtained in (2) above and obtaining the height of the highest point from the SUS plate, the value of warpage asked for The degree of warpage was evaluated as "◯" when less than 1 cm, "Δ" when 1 cm or more and less than 3 cm, and "×" when 3 cm or more.

<Test Example 3: Evaluation of copper foil adhesion (peel strength)>
(1) Surface treatment of copper foil The shiny side of the copper foil "3EC-III (thickness 35 μm)" manufactured by Mitsui Mining & Smelting Co., Ltd. is immersed in MEC Etch Bond "CZ-8101" manufactured by MEC Co., Ltd. to roughen the copper surface ( Ra value=1 μm), and an antirust treatment (CL8300) was applied. This copper foil is called CZ copper foil. Further, heat treatment was performed in an oven at 130° C. for 30 minutes.

(2) Lamination of copper foil and formation of an insulating layer The resin sheet B prepared in Preparation Example 2 is subjected to a batch type vacuum pressure laminator (manufactured by Nikko Materials Co., Ltd., 2-stage build-up laminator, CVP700) to obtain a resin composition. Both sides of the inner layer circuit board were laminated so that the material layer was bonded to the inner layer circuit board. The lamination process was carried out by pressure bonding for 30 seconds at 100° C. and pressure of 0.74 MPa after reducing the pressure to 13 hPa or less for 30 seconds. The PET film as the support was peeled off from the laminated resin composition layer. The treated surface of the "3EC-III" CZ copper foil was laminated on the resin composition layer under the same conditions as above. Then, a sample was produced by curing the resin composition layer under curing conditions of 190° C. for 90 minutes to form an insulating layer.

(3) Measurement of Copper Foil Peeling Strength (Adhesion) Before Accelerated Environmental Test (HAST) The sample prepared above was cut into small pieces of 150×30 mm. Using a cutter, cut the copper foil portion of the small piece into a portion with a width of 10 mm and a length of 100 mm. -50C-SL"), and using an Instron universal testing machine, at room temperature, measure the load when peeling off 35 mm in the vertical direction at a speed of 50 mm / min in accordance with JIS C6481, The pre-HAST peel strength (kgf/cm) was used.

(4) Measurement of copper foil peeling strength (adhesion) after accelerated environmental test (HAST) The sample prepared above was tested at 130°C and 85°C using a highly accelerated life tester (“PM422” manufactured by ETAC). % relative humidity and 3.3 V DC voltage applied for 200 hours. After that, one end of the copper foil is peeled off and gripped with a gripper (Autocom type testing machine "AC-50C-SL" manufactured by TSE Co., Ltd.), using an Instron universal testing machine, The load when 35 mm was peeled off vertically at a rate of 50 mm/min was measured in accordance with JIS C6481, and the peel strength after HAST (kgf/cm) was obtained. In addition, when the peel strength after HAST was over 0.35 kgf/cm, it was evaluated as "◯", and when it was 0.35 kgf/cm or less, it was evaluated as "x".

<Test Example 4: Evaluation of Plating Adhesion>
(1) Surface treatment of inner layer circuit board Both sides of a glass cloth base epoxy resin double-sided copper clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic R1515A) on which an inner layer circuit is formed The copper surface was roughened by etching with CZ8101 to a depth of 1 μm.

(2) Lamination of support-attached resin sheet The protective film was peeled off from the resin sheet B prepared in Production Example 2, and a batch-type vacuum pressure laminator (manufactured by Nikko Materials Co., Ltd., two-stage build-up laminator, CVP700) was used. , laminated on both sides of the inner layer circuit board. Lamination was carried out by pressure bonding for 45 seconds at 130° C. and a pressure of 0.74 MPa after reducing the pressure for 30 seconds to an atmospheric pressure of 13 hPa or less. Then, hot pressing was performed at 120° C. and a pressure of 0.5 MPa for 75 seconds.

(3) Curing of Resin Composition The laminated resin composition layer was continuously cured at 130° C. for 30 minutes and then cured at 170° C. for 30 minutes to form an insulating layer.

(4) Via hole formation CO ₂ laser processing machine ("605GTWIII (-P)" manufactured by Mitsubishi Electric) is used to irradiate the insulating layer with a laser beam to form a top diameter (diameter) of about 30 μm on the insulating layer. A plurality of via holes were formed. The irradiation conditions of the laser light were mask diameter 1 mm, pulse width 16 μs, energy 0.2 mJ/shot, number of shots 2, and burst mode (10 kHz).

(5) Roughening treatment The inner layer circuit board on which the insulating layer is formed is soaked in a swelling liquid, Swelling Dip Securigant P (an aqueous solution of glycol ethers and sodium hydroxide) containing diethylene glycol monobutyl ether from Atotech Japan Co., Ltd. immersed at 60° C. for 10 minutes, then immersed in Concentrate Compact P (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) of Atotech Japan Co., Ltd. as a roughening solution at 80° C. for 20 minutes; Finally, as a neutralizing solution, it was immersed in Reduction Shoryusin Securigant P (an aqueous solution of sulfuric acid) available from Atotech Japan Co., Ltd. at 40° C. for 5 minutes, and then dried at 80° C. for 30 minutes. This board was designated as "evaluation board A".

(6) Plating by Semi-Additive Method Evaluation board A was immersed in an electroless plating solution containing PdCl ₂ at 40° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25° C. for 20 minutes. After annealing by heating at 150° C. for 30 minutes, an etching resist was formed, and after pattern formation by etching, copper sulfate electroplating was performed to form a conductor layer with a thickness of 20 μm. Annealing was then performed at 200° C. for 60 minutes. This board was designated as "evaluation board B".

(7) Measurement of peeling strength (adhesion) of the plated conductor layer The conductor layer of the evaluation board B was cut with a width of 10 mm and a length of 100 mm. E, Autocom type testing machine AC-50C-SL), and measured the load when peeling off 35 mm in the vertical direction at a speed of 50 mm / min at room temperature, plating peel strength (kgf / cm ).

<Test Example 5: Evaluation of Small Diameter Via Formability>
For the roughened substrate A obtained in the step (4) of Test Example 1, via hole openings were formed in an insulating layer having a thickness of 10 μm with a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, S-4800). We also observed the via holes after the roughening treatment. Then, from the observed SEM image, an arbitrary diameter 2L _1t of the circular opening surface of the via hole after the roughening treatment and a diameter 2L _2t perpendicular thereto were measured, and substituted into the formula of top area S _t =πL _1t L _2t . to calculate the top area _St. Calculation of the top area S _t was performed at five randomly selected via holes. The average value of the top areas of five via holes was taken as the average top area _Sta .

Similarly, an arbitrary diameter 2L _1b of the circular bottom surface of the via hole after the roughening treatment and a diameter 2L _2b perpendicular thereto are measured, and the bottom area S b is substituted into the formula of bottom area S _b =πL _1b L _2b to obtain the bottom area S _b . Calculated. Similarly, the calculation of the bottom area _Sb was performed for five randomly selected via holes. The average value of the bottom areas _Sb of five via holes was taken as the average bottom area _Sba .

From the average top area S _ta and the average bottom area S _ba obtained above, the average area ratio (the ratio of the average top area S _ta to the average bottom area S _ba "S _ta /S _ba ") was calculated. If the average area ratio S _ta /S _ba is 60% or more, "◯", if the average area ratio S _ta /S _ba is 50% or more and less than 60%, "△", The average area ratio S _ta /S _ba is less than 50% was determined as "x".

Table 1 below shows the amounts of non-volatile components used in the resin compositions of Examples and Comparative Examples, the measurement results and evaluation results of Test Examples, and the like.

A resin composition comprising (A) an epoxy resin, (B) an inorganic filler, and (C) a particulate or non-particulate elastomer, wherein the component (B) has a specific surface area of 10 m ² /g or more, By using a resin composition in which the content of component (C) is 35% by mass or less and the average particle diameter of component (C) is 0.8 μm or less, warpage of the cured product can be suppressed and excellent It was found that insulation reliability, adhesion, and formation of small-diameter vias could be achieved.

Claims (10)

A resin composition comprising (A) an epoxy resin, (B) an inorganic filler, and (C) a non-particulate elastomer,
(B) component has a specific surface area of 10 m ² /g or more,
The content of the component (B) is 40% by mass or more when the non-volatile component in the resin composition is 100% by mass,
The content of the component (C) is 27 % by mass or less when the non-volatile components other than the component (B) in the resin composition are taken as 100% by mass,
A resin composition in which the component (C) has a functional group capable of reacting with the component (A). 2. The resin composition according to claim 1 , wherein the component (B) has a specific surface area of 20 m ^<2> /g or more. 3. The resin composition according to claim 1 , wherein the component (B) is silica. The content of component (C) is 25% by mass or less when non-volatile components other than component (B) in the resin composition are 100% by mass . Resin composition. The content of component (C) is 1% by mass or more when non-volatile components other than component (B) in the resin composition are 100% by mass . Resin composition. A cured product of the resin composition according to any one of claims 1 to 5 . A sheet-like laminate material containing the resin composition according to any one of claims 1 to 5 . A resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of claims 1 to 5 provided on the support. A printed wiring board comprising an insulating layer comprising a cured product of the resin composition according to any one of claims 1 to 5 . A semiconductor device comprising the printed wiring board according to claim 9 .